EP1492754B1 - Verfahren zur herstellung von carbonsäuren - Google Patents

Verfahren zur herstellung von carbonsäuren Download PDF

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Publication number
EP1492754B1
EP1492754B1 EP03745809A EP03745809A EP1492754B1 EP 1492754 B1 EP1492754 B1 EP 1492754B1 EP 03745809 A EP03745809 A EP 03745809A EP 03745809 A EP03745809 A EP 03745809A EP 1492754 B1 EP1492754 B1 EP 1492754B1
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EP
European Patent Office
Prior art keywords
oxidation
hydroperoxide
process according
catalyst
cyclohexane
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Expired - Lifetime
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EP03745809A
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English (en)
French (fr)
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EP1492754A2 (de
Inventor
Didier Bonnet
Eric Fache
Jean-Pierre Simonato
Serge Veracini
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Rhodia Polyamide Intermediates SAS
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Rhodia Polyamide Intermediates SAS
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/14—Adipic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/21—Dicarboxylic acids containing twelve carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings

Definitions

  • the present invention relates to a process for producing carboxylic acids by oxidation of an alkyl hydroperoxide compound.
  • It relates more particularly to the oxidation of cyclohexyl hydroperoxide to adipic acid by an oxidizing agent containing molecular oxygen.
  • adipic acid is an important chemical compound used as a raw material in many fabrications such as the production of polymers such as polyamides, polyesters or polyurethanes.
  • Processes for the oxidation of hydrocarbons to dicarboxylic acids by two successive stages of oxidation are used industrially on a large scale. These processes consist, in a first step, of carrying out the oxidation of hydrocarbons to alcohols and ketones by oxygen or an oxygen-containing gas. In a second step, the alcohols and / or ketones are oxidized to acids by nitric oxidation. Different embodiments of these two steps are exploited.
  • the first step may comprise two substeps, in a first substep the hydrocarbon is oxidized to hydroperoxide. After separation of the hydroperoxide from the unreacted hydrocarbon, the hydroperoxide is decomposed in a separate reactor of alcohol and / or ketone. In another embodiment also exploited, the production of hydroperoxide and its decomposition into alcohol and / or ketone are carried out simultaneously in a single reactor.
  • the patent US 3361806 describes a process for the oxidation of a mixture of cyclohexanone, cyclohexanol and oxygenates.
  • One of the aims of the present invention is to propose a process for the oxidation of hydrocarbons to produce acids or polyacids, not requiring the use as an oxidizing agent of nitric acid or a derivative thereof and therefore not producing of nitrogen oxides.
  • the invention provides a process for producing carboxylic acids, which comprises reacting a hydrocarbon hydroperoxide with oxygen or an oxygen-containing gas in the presence of a catalyst.
  • oxidizing composition comprising a metal belonging to the groups of transition metals.
  • the catalyst may advantageously comprise a metal element selected from the group consisting of Cu, Ag, Au, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Al, Sc, In, Ti, Y, Ga, Ti, Zr, Hf. , Ge, Sn, Pb, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Bones, Co, Rh, Ir, Ni, Pd, Pt, lanthanides as this and combinations of these.
  • a metal element selected from the group consisting of Cu, Ag, Au, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Al, Sc, In, Ti, Y, Ga, Ti, Zr, Hf. , Ge, Sn, Pb, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Bones, Co, Rh, Ir, Ni, Pd, Pt, lanthanides as this and combinations of these.
  • catalytic elements are used either in the form of compounds advantageously at least partially soluble in the liquid oxidation medium under the conditions for carrying out the oxidation reaction, or supported, absorbed or bound to an inert support such as silica alumina, for example.
  • the catalytically active metal elements are supported or incorporated in a micro or mesoporous mineral matrix or in a polymer matrix or are in the form of organometallic complexes grafted onto an organic or inorganic support.
  • the metal is an element of the support or that one works with complexes sterically trapped in porous structures under the conditions of oxidation.
  • the homogeneous or heterogeneous catalyst consists of groups IVb (Ti group), Vb (V group), Vlb (Cr group), Vllb (IV group) metal salts or complexes ( Mn group), VIII (Fe or Co or Ni group), Ib (Cu group), and cerium, alone or in a mixture.
  • Preferred elements are, in particular, Co and / or Mn and / or Cr and / or Zr, Hf, Ce and / or Zr, Hf.
  • the concentration of metal in the liquid oxidation medium varies between 0.00001 and 5% (% by weight), preferably between 0.0001% and 2%.
  • the hydroperoxides which are used in the process of the invention are generally the primary or secondary hydroperoxides derived from alkanes, cycloalkanes or alkylaromatic hydrocarbons whose aromatic ring optionally comprises one or more substituents.
  • substituents such as in particular alkyl group or halogen atom more particularly chlorine atom, alkenes and cycloalkenes having from 3 to 20 carbon atoms.
  • hydroperoxides By way of examples of such hydroperoxides, mention may be made of cyclohexyl hydroperoxide, cyclododecyl hydroperoxide, tetralin hydroperoxide, ethylbenzene hydroperoxide and pinane hydroperoxide.
  • hydroperoxides one of the most interesting is certainly the cyclohexyl hydroperoxide whose oxidation leads to adipic acid as predominant dicarboxylic acid, one of the basic compounds for the manufacture of polyamides, more particularly polyhexamethyleneadipate .
  • hydroperoxides can be obtained by different processes and used in the process of the invention in purified form or in admixture with other compounds originating in particular from their manufacturing processes.
  • the process of the invention may be carried out preferably in the presence of a solvent advantageously constituted by the hydrocarbon used for the manufacture of the hydroperoxide.
  • a solvent advantageously constituted by the hydrocarbon used for the manufacture of the hydroperoxide.
  • various solvents such as alkanes, among which mention will be made more particularly of hexane, heptane and isooctane; cycloalkanes, among which mention will be made by way of illustration of cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons, alcohols, ketones, ethers, ntriles, carboxylic acids such as acetic acid and mixtures of these solvents
  • the hydroperoxide is generally produced in the form of a solution in a hydrocarbon, for example cyclohexane, by oxidation thereof, the oxidation reaction is advantageously carried out on a solution originating from oxidation of the hydrocarbon (cyclohexane).
  • This solution can be used in the state or after elimination of certain constituents in a manner known per se. It is also possible to use a solution of hydroperoxide in the solvent, for example, substantially pure cyclohexane.
  • the process of the invention may be carried out on a solution originating from the oxidation of a hydrocarbon to hydroperoxide as it is or after removal of certain by-products by, for example, washing the solution with water for in particular, removing the water-soluble acids or the purified hydroperoxide by conventional purification methods such as distillation, extraction or any other conventional method.
  • the oxidation reaction is carried out at a temperature between 50 ° C and 250 ° C, preferably between 70 ° C and 200 ° C. It can be carried out under atmospheric pressure. However, it is generally carried out under pressure to maintain the components of the reaction medium in liquid form.
  • the pressure can be between 10 KPa (0.1 bar) and 20000 KPa (200 bar), preferably between 100 Kpa (1 bar) and 10000 Kpa (100 bar).
  • the oxygen used may be in pure form or in admixture with an inert gas such as nitrogen or helium. It is also possible to use air that is more or less enriched with oxygen.
  • the oxidation process can be carried out continuously or in a batch process.
  • the liquid reaction medium leaving the reactor is treated according to known methods allowing firstly to separate and recover the acids produced and secondly to recycle unoxidized or partially oxidized organic compounds such as cyclohexane, cyclohexanol and / or cyclohexanone, the catalyst and optionally the solvent.
  • the amount of catalyst is generally between 0.00001% and 5% and preferably between 0.0001% and 2%, without these values being critical. However, it is a matter of having sufficient activity while not using excessive amounts of a catalyst which must then be separated from the final reaction mixture and recycled.
  • an initiator compound of the oxidation reaction such as, for example, a ketone, an aldehyde or a hydroperoxide.
  • Cyclohexanone which is a reaction intermediate in the case of the oxidation of cyclohexane, is particularly indicated.
  • the initiator represents from 0.01% to 20% by weight of the weight of the reaction mixture used, without these proportions having a critical value.
  • the initiator is especially useful when starting the oxidation and when the oxidation is carried out at a temperature below 120 ° C. It can be introduced at the beginning of the reaction.
  • reaction medium another compound which may in particular have the effect of improving the productivity and / or the selectivity of the oxidation reaction in acid.
  • adipic such as improving the solubilization of oxygen.
  • Lipophilic carboxylic acids suitable for the invention include hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, stearic acid (octadecanoic acid) and their permethylated derivatives (total substitution of the hydrogens of the methylenes groups by methyl group), 2-octadecylsuccinic acid, 2,5-ditertiobutylbenzoic acid, 4-tert-butylbenzoic acid, 4-octylbenzoic acid, tert-butyl hydrogenorthophthalate, naphthenic or anthracene acids substituted with alkyl groups, preferably of tert-butyl type, substituted derivatives of phthalic acids, fatty diacids such as dimer of fatty acid.
  • Acids belonging to the preceding families and carrying different substituents electrodonorers (groups with heteroatom type O or N) or electroacceptors (halogens, sulfonimides, nitro groups, sulfonanato or the like) may also be mentioned.
  • reaction mixture resulting from the oxidation is subjected to various operations of separation of some of its components to, for example, allow their recycling at the level of oxidation and the recovery of the acids produced.
  • the raw reaction mixture can first be subjected to cooling at a temperature of, for example, 16 ° C. to 30 ° C., which causes the crystallisation of at least a portion of the acid. form.
  • the catalyst may be in one of the organic phases if it is soluble in said phase, or in the lower aqueous phase.
  • the organic and aqueous liquid phases constituting the filtrate or the centrifugate are optionally separated by decantation: the organic phase (s) can be recycled in a new oxidation reaction.
  • the final crude reaction mixture can be extracted while hot, for example at a temperature of up to 75.degree.
  • the reaction mixture then decants in at least two liquid phases: one or more organic phases essentially containing the unreacted hydrocarbon, the solvent, the oxidation intermediates and an aqueous liquid phase essentially containing the formed acids and the formed water.
  • the organic phase or phases may be present in the organic phase or phases, recovered by solid / liquid separation before precipitation or crystallization of the acid formed in the case of heterogeneous catalysis or if it is soluble.
  • in the aqueous phase extracted by liquid / liquid extraction, on resin or electrodialysis.
  • the liquid phases are separated or the organic phases can be recycled in a new oxidation reaction.
  • water may be added to the reaction medium to obtain a better dissolution of acid byproducts of oxidation and better recovery of the acid formed.
  • Recovery of the acid is generally carried out by precipitation during cooling of the reaction medium.
  • the acid thus recovered can be purified according to standard techniques and described in numerous patents. By way of example, mention may be made of French patents 2749299 and 2749300 .
  • the non-organic or aqueous liquid phase contains the catalyst, it is extracted either before crystallization of the acid formed by precipitation or extraction according to known methods such as liquid-liquid extraction, electrodialysis, treatment with exchange resins or for example, after crystallization of the acid formed by extraction techniques described above or the like.
  • the invention also relates to a carboxylic acid production process consisting in a first step of oxidizing a hydrocarbon to hydroperoxide with oxygen or an oxygen-containing gas.
  • the medium obtained, after optional concentration by evaporation of a portion of the unreacted hydrocarbon, is subjected to a second step of oxidation of the hydroperoxide to carboxylic acids in accordance with the process of the invention described above. .
  • the reaction medium resulting from the first oxidation step is subjected to different separation treatments and elimination of by-products to purify the hydroperoxide.
  • These treatments may include washing the oxidation medium with water or a slightly basic solution.
  • the autoclave is immediately pressurized to 100 bar of room temperature air and placed in an oven.
  • the mixture is heated to 130 ° C with shaking.
  • the autoclave is immediately pressurized to 100 bar of room temperature air and placed in an oven.
  • the mixture is heated to 130 ° C with shaking.
  • the autoclave is immediately pressurized to 100 bar of room temperature air and placed in an oven.
  • the mixture is heated to 130 ° C with shaking.
  • the autoclave is immediately pressurized to 100 bar of room temperature air and placed in an oven.
  • the mixture is heated to 130 ° C with shaking.
  • the autoclave is immediately pressurized to 100 bar of room temperature air and placed in an oven.
  • the mixture is heated to 130 ° C with shaking.
  • the autoclave is immediately pressurized to 100 bar of room temperature air and placed in an oven.
  • the mixture is heated to 130 ° C with shaking.
  • the autoclave is immediately pressurized to 75 bar of room temperature air.
  • the reactor is then heated to 130 ° C. and then connected to an oxygen supply providing, during the reaction time, an oxygen partial pressure of 20 bar for a total pressure of the autoclave of 100 bar.
  • the whole is subjected for the duration of the reaction to stirring at 1000 rpm.
  • the autoclave is immediately pressurized to 75 bar of room temperature air.
  • the reactor is then heated to 130 ° C. and then connected to a supply of oxygen which, during the reaction time, provides an oxygen partial pressure of 20 bar for total pressure of the autoclave of 100 bar.
  • the whole is subjected for the duration of the reaction to stirring at 1000 rpm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (18)

  1. Verfahren zur Herstellung von Carbonsäuren, dadurch gekennzeichnet, dass man ein organisches Hydroperoxid, das durch Oxidation von Alkanen. Cycloalkanen oder alkylaromatischen Kohlenwasserstoffen erhalten wurde, mit einem Oxidationsmittel, welches molekularen Sauerstoff einschließt, und in Gegenwart eines Oxidationskatalysators nach Abtrennung der Nebenprodukte, die anders sind als die Hydroperoxidverbindung der Oxidation von Alkanen, Cycloalkanen oder alkylaromatischen Kohlenwasserstoffen, reagieren lässt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das organische Hydroperoxid aus der Gruppe ausgewählt ist, die die primären oder sekundären Hydroperoxide einschließt, die sich von Alkanen, Cycloalkanen, alkylaromatischen Kohlenwasserstoffen, deren aromatischer Cyclus gegebenenfalls einen oder mehrere Substituenten einschließt, wie insbesondere eine Alkylgruppe oder ein Halogenatom, ganz besonders ein Chloratom, Alkenen und Cycloalkenen mit 3 bis 20 Kohlenstoffatomen ableiten.
  3. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass das organische Hydroperoxid aus der Gruppe ausgewählt ist, die Cyclohexylhydroperoxid, Cyclododecylhydroperoxid. Tetralinhydroperoxid. Ethylbenzolhydroperoxid, Pinanhydroperoxid einschließt.
  4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Reaktionsmedium, das aus der Oxidation eines Kohlenwasserstoffs hervorgeht, einer Wäsche mit Wasser unterzogen wird, bevor es mit einem Oxidationsmittel zur Reaktion gebracht wird.
  5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Katalysator in dem flüssigen Medium unter den Bedingungen der Durchführung der Oxidationsreaktion löslich ist.
  6. Verfahren nach einem der Ansprüche 1 bis 4. dadurch gekennzeichnet, dass der Katalysator in dem flüssigen Medium unter den Bedingungen der Durchführung der Oxidationsreaktion unlöslich ist.
  7. Verfahren nach Anspruch 6. dadurch gekennzeichnet, dass der Katalysator ein geträgerter Katalysator ist, der einen mineralischen oder polymeren Träger einschließt.
  8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Oxidationsreaktion in Gegenwart eines Lösungsmittels durchgeführt wird.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass das Lösungsmittel aus der Gruppe ausgewählt ist, die Alkane, Cycloalkane, aromatische Kohlenwasserstoffe, halogenierte Kohlenwasserstoffe, Alkohole, Ketone, Ether und Gemische dieser Lösungsmittel einschließt.
  10. Verfahren nach Anspruch 9. dadurch gekennzeichnet, dass das Lösungsmittel aus der Gruppe ausgewählt ist, die Hexan, Heptan, Isooctan, Cyclohexan, Cyclooctan, Benzol, Toluol und Xylol einschließt.
  11. Verfahren nach Anspruch 10. dadurch gekennzeichnet, dass das Lösungsmittel der Kohlenwasserstoff ist, der dem zu oxidierenden Hydroperoxid entspricht.
  12. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das flüssige Medium, nach Oxidation, in mindestens eine organische Phase, die durch nicht oxidiertes Hydroperoxid gebildet wird, das Lösungsmittel und eine wässrige oder feste Phase dekantiert wird, wobei die organischen Phasen in eine neue Oxidation recycelt werden, wobei die produzierte Säure aus der wässrigen Phase extrahiert wird.
  13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass die Säure aus der wässrigen Phase durch Kristallisation extrahiert wird.
  14. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Katalysator mit der oder den organischen Phasen recycelt wird.
  15. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Katalysator von dem flüssigen Medium durch Dekantieren oder Fest/Flüssig-Trennung abgetrennt wird.
  16. Verfahren nach einem der Ansprüche 10 oder 11, dadurch gekennzeichnet, dass der in der wässrigen Phase lösliche Katalysator durch Flüssig/Flüssig-Extraktion, Trennung über Harze oder durch Elektrodialyse extrahiert wird.
  17. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Katalysator Mangan als katalytisch aktives Element einschließt.
  18. Verfahren zur Herstellung von Carbonsäuren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das organische Hydroperoxid durch Oxidation von Alkanen, Cycloalkanen oder alkylaromatischen Kohlenwasserstoffen durch Sauerstoff oder ein Gas erhalten wird, das Sauerstoff enthält, wobei das Oxidationsreaktionsmedium vor der Oxidation der Hydroperoxide zu Carbonsäuren durch Extraktion von mindestens einem Teil der Alkane, Cycloalkane oder alkylaromatischen nicht oxidierten Kohlenwasserstoffe, an Hydroperoxid konzentriert wird.
EP03745809A 2002-04-08 2003-03-28 Verfahren zur herstellung von carbonsäuren Expired - Lifetime EP1492754B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0204332A FR2838122B1 (fr) 2002-04-08 2002-04-08 Procede de fabrication d'acides carboxyliques
FR0204332 2002-04-08
PCT/FR2003/000984 WO2003084913A2 (fr) 2002-04-08 2003-03-28 Procede de fabrication d'acides carboxyliques

Publications (2)

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EP1492754A2 EP1492754A2 (de) 2005-01-05
EP1492754B1 true EP1492754B1 (de) 2008-11-05

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EP03745809A Expired - Lifetime EP1492754B1 (de) 2002-04-08 2003-03-28 Verfahren zur herstellung von carbonsäuren

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EP (1) EP1492754B1 (de)
JP (1) JP4434751B2 (de)
KR (1) KR100641623B1 (de)
CN (1) CN100341837C (de)
AT (1) ATE413372T1 (de)
AU (1) AU2003232303A1 (de)
BR (2) BRPI0308954B8 (de)
DE (1) DE60324536D1 (de)
ES (1) ES2315520T3 (de)
FR (1) FR2838122B1 (de)
RU (1) RU2297997C2 (de)
TW (1) TWI334863B (de)
UA (1) UA77771C2 (de)
WO (1) WO2003084913A2 (de)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE757061A (fr) * 1969-10-06 1971-04-05 Rhone Poulenc Sa Procede d'obtention d'acide adipique
JPS52931B1 (de) * 1970-06-27 1977-01-11
GB9113343D0 (en) * 1991-06-20 1991-08-07 Shell Int Research Catalytic oxidation of hydrocarbons
US5321157A (en) * 1992-09-25 1994-06-14 Redox Technologies Inc. Process for the preparation of adipic acid and other aliphatic dibasic acids
EP0784045B1 (de) * 1996-01-13 2000-08-23 Council of Scientific and Industrial Research Verfahren zur Herstellung von Adipinsäure
DE19941315A1 (de) * 1999-08-31 2001-03-01 Bayer Ag Selektivoxidation von Kohlenwasserstoffen

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Publication number Publication date
FR2838122B1 (fr) 2004-05-21
KR20040111498A (ko) 2004-12-31
RU2297997C2 (ru) 2007-04-27
ES2315520T3 (es) 2009-04-01
AU2003232303A1 (en) 2003-10-20
TWI334863B (en) 2010-12-21
ATE413372T1 (de) 2008-11-15
EP1492754A2 (de) 2005-01-05
WO2003084913A3 (fr) 2004-04-01
BR0308954A (pt) 2005-01-04
JP4434751B2 (ja) 2010-03-17
JP2005522474A (ja) 2005-07-28
BR0308954B1 (pt) 2013-11-19
DE60324536D1 (de) 2008-12-18
CN100341837C (zh) 2007-10-10
RU2004132831A (ru) 2005-07-20
WO2003084913A2 (fr) 2003-10-16
KR100641623B1 (ko) 2006-11-06
UA77771C2 (en) 2007-01-15
TW200306300A (en) 2003-11-16
AU2003232303A8 (en) 2003-10-20
FR2838122A1 (fr) 2003-10-10
CN1649818A (zh) 2005-08-03
BRPI0308954B8 (pt) 2016-10-11
BRPI0308954C8 (pt) 2017-03-21
WO2003084913A8 (fr) 2004-06-10

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